Antioxidative Wirksamkeit von Tocochromanolen – Rangfolgebestimmung mit „Response Surface Methodology (RSM)”︁

Antioxidative Efficiency of Tocochromanols – Determination of the Sequence with ?Response Surface Methodology RSM)”? By a model study four tocopherols: α-T, β-T, γ-T and δ-T as well as the ex latice Heveae brasiliensis isolated three tocotrienols-(T₃): α-T₃, γ-T₃, and δ-T₃ were investigated on their antioxidative efficiencies to protect linoleic acid methyl ester. With fixed temperatures and appointed oxygen supply resulted from repeated measurements the values of the standard deviations of the dates. For each of the seven tocochromanols by using Response Surface Methodology as statistical Method a regression equation was formulated and further by multiple regression analysis evaluated and at last by 3-D-response surface graphically represented. So it is possible to present synoptically all the area of experience known by the variable conditions of the several experiments. A ranking of the tocochromanols depends on the choosen conditions for temperature and oxygen. Only δ-T was even effective by a residual amount of 25% in spite of the extreme condition of 80°C/20% O₂ within 6 hours.     

Polymorphism and crystallization in poly(vinylidene fluoride)/ poly(ϵ‐caprolactone)–block–poly(dimethylsiloxane)–block–poly(ϵ‐caprolactone) blends

The miscibility, crystallization kinetics and crystalline morphology of a new system of poly(vinylidene fluoride)/poly(?‐caprolactone)‐block‐poly(dimethylsiloxane)‐block‐poly(?‐caprolactone) (PVDF/PCL‐b‐PDMS‐b‐PCL) triblock copolymer were investigated by a variety of techniques. The miscibility and phase behaviour of PVDF/PCL‐b‐PDMS‐b‐PCL were studied by determination of the melting point temperature, crystallization kinetics and Fourier transform infrared (FTIR) mapping. Chemical imaging was used as a new technique to characterize the interaction of polymer blends in crystalline morphology. The results demonstrate the existence of characteristic peaks of both PVDF and PCL in the chosen crystalline area. The crystalline structures of PVDF were affected by the PCL‐b‐PDMS‐b‐PCL triblock copolymer and facilitate the formation of the β polymorph which was illustrated by FTIR analysis. The β crystal phase fraction increases significantly on increasing the composition of the PCL‐b‐PDMS‐b‐PCL triblock copolymer. In addition, confined crystallization of PCL within PVDF inter‐lamellar and/or inter‐fibrillar regions was confirmed through polarizing optical microscopy, wide‐angle X‐ray diffraction and small‐angle X‐ray scattering analysis. © 2019 Society of Chemical Industry     

Thermal stability of “living” polymer–lithium systems

The thermal stabilities of polybutadienyllithium, polyisoprenyllithium, and polystyryllithium solutions have been determined in hydrocarbon solvents. Kinetic analysis indicated that a complex mechanism was involved in the thermolysis of polybutadienyllithium. The thermal stability was observed to increase with increasing lithium concentration, suggesting the presence of competitive reactions in addition to the expected elimination of lithium hydride. The thermal stability of the three systems studied was consistent with their reported degrees of association: dimeric polystyryllithium was less stable than tetrameric polyisoprenyllithium or hexameric polybutadienyllithium.     

On the so-called “semi-ionic” C–F bond character in fluorine–GIC

The short-range structures of fluorine–graphite intercalation compounds with stage-1 structures, C_xF (x = 2.47, 2.84, 3.61), were analyzed by means of neutron diffraction. It has been shown that the so-called “semi-ionic” C–F bond character in C_xF is essentially covalent with the bond length of 0.140 nm, and the original planar graphene sheets are buckled at the sp³-hybridized carbon atoms bound to fluorine atoms. Conjugated C–C double bonds with the bond length of 0.142 nm are preserved between the carbon atoms unbound to fluorine atoms in C_xF, while other C–C bonds are single bonds with the bond lengths of 0.153 nm. The C–F bond order in C_xF is slightly lower than those in poly(carbon monofluoride) ((CF)_n) and poly(dicarbon monofluoride) ((C₂F)_n), which is explained by the hyperconjugation involving the C–C bonds on the carbon sheets and C–F bond.     

Properties and structure of PVP–lignin “blend films”

Blend films of poly (4‐vinylpyridine) and lignin were prepared by the casting method. Their structure and properties were studied by Fourier transform infrared (FTIR), wide‐angle X‐ray diffraction (WXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TG), and differential scanning calorimetry (DSC). The IR spectra of the blend films indicated that hydrogen‐bonding interaction occurred between poly (4‐vinylpyridine) and lignin. The glass transition temperature of these blends increased with the increase of lignin content, which indicated that these blends were able to form a miscible phase due to the formation of intermolecular hydrogen bonding between the hydroxyl of lignin and the pyridine ring of poly (4‐vinylpyridine). The thermostability of these blends decreased with the increase of lignin content. Initially, an appreciable increase in the measured tensile strength was achieved with a lignin content of 15%, at which the maximum value of 33.03 MPa tensile strength was reached. At a 10% lignin incorporation level, the blend film exhibited a maximum value of 9.03% strain. When the threshold in lignin content for blend films exceeded that limit of 10% lignin, the strain behavior of these blend films deteriorated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1405–1411, 2005     

Healing clays: Mineralogical and geochemical constraints on the preparation of clay–water suspension (“argillic water”)

Clays have been long taken internally due to their sorption effects and the mechanical shielding developed by sheet morphologies. The purpose of this paper is the modelling of the mentioned traditional application in terms of chemical and mineralogical budget towards the body.Four polymineralic clays potentially suitable for therapeutic use were analysed for their mineralogical and geochemical composition. Quartz is always present, as well as feldspars, whereas carbonates are more variable (from trace levels, to about 40%). The clay mineralogy is characterised by mixed layers illite–smectite, kaolinite and illite. Most chemical elements show little anomalies compared to average shale [Turekian, K.K., Wedephol, K.H., 1961. Distribution of the elements in some major units of the earth's crust. Geological Society of America Bulletin, 72, 175–192], excluding Ca that is enriched according to the carbonate occurrence. Another geochemical feature is the depletion of more electronegative elements, among which very hazardous elements may be found.For the preparation of “argillic water”, the clays were dispersed in water and three suspensions were prepared to test the effect of settling time (5 min, 1 h, and 24 h). After the settling, the supernatant was centrifuged to analyse the solution and the particulate. The grinding of clays (a common practice for industrial uses) sensibly reduce the mineralogical selectivity of settling, nevertheless, quartz and feldspars are depleted during settling and phyllosilicates are enriched or fluctuate when the starting value is high; the carbonate content increases or decrease within a narrow interval. The grinding procedure minimises the different behaviour of clay minerals dispersed in water because the clay assemblage of suspended particulate does not show significant trends; only illite shows a slightly decrease.The solute composition is dominated by Na > Si > Ca > K > Mg. The comparison of the 4 clays indicates that the sample richest in mixed layers shows the highest content of many trace elements in solution. The variations of solution chemistry indicate that the less soluble elements decrease with the time of settling (e.g. Fe, Al, Mn): the elements hosted in organic matter or sulphides and soluble in oxidative media, increase with time (V, Mo, Sb, As). Many other elements are rather constant or at very low concentrations. The occurrence of sorptive minerals tends to hide these trends mainly during the first hour of settling.The chemical input to the body was calculated adding the amount of element in solution to the extractable amount from the digestion of particulates. The latter is based on the simulated digestion of clays taken from the literature. A critical point is the definition of a threshold that discriminates between useful and excessive ingestion of chemical elements. Since no reference models are available, the limit for drinking water was used. Considering that adults drink 2 l of water, the maximum daily dose for water was transformed into the amount of each chemical element considered by the law and compared with the amount available from the preparation of “argillic water”. Based on these results, the settling of clays can be tuned in order to emphasise the desired composition or to minimise side effects.     

Spiegelsymmetrische Hexahydro-1,2,4,5-tetrazine aus Pyrazolidon-(3)-N,N-betainen – ein Beitrag zur „thermischen Dimerisierung”︁ von 1,3-Dipolen

Mirror-symmetric Hexahydro-1,2,4,5-tetrazines from Pyrazolidine-3-one-N,N-betaines—a Contribution to the „Thermal Dimerization”︁ of 1,3-Dipoles Chemical reactions, i.r., ¹H-n.m.r., and ¹³C-n.m.r. data show that the “thermal dimers” of pyrazolidine-3-one azomethinimines 2 , which till now accidentally formed during the synthesis of 2 from pyrazolidine-3-ones 5 and aldehydes 6 , are 5,11-diaryl-perhydro-dipyrazolo[1,2-a; 1′,2′-d][1,2,4,5]-tetrazine-1,9-diones 3 , i.e. mirror-symmetric hexahydro-1,2,4,5-tetrazines with (C-5) and (C-11) placed on the mirror plane. From DREIDING models and from the nonequivalence, concerning ¹³C-n.m.r., of the pairs of carbon atoms in the o- resp. m-positions of the aryl substituent I at (C-5) of the “dimers” 3 is derived that the rotation of I is sterically hindered (ΔG = 16,3 kcal/mole for 3b ), and that the preferred arrangement of I is perpendicular to the plane of the hexahydrotetrazine ring. The “thermal dimerization” of the 1,3-dipoles 2 is a complex series of two addition and elimination steps proceeding in the presence of catalytical amounts of pyrazolidine-3-one 5 and of H^⊕. The mechanism is rationalized, consequences are suggested concerning known “dimerizations” of 1,3-dipoles.     

4–Hydroxy–3–arylamino–l, 8–naphthalimides and 3–(and 4–) hydroxy–2–(and 5–) arylamino–7H–bcnzimidazo–(2, l–a)benz(d,e)isoquinolin–7–ones. Red dyes for synthetic–polymer fibres

4–Hydroxy–1, 8–naphthalimides and the isomer mixtures of'3–and 4–hydroxy–7 H–benzimidazo–(2, l–a)–benz(d, e)–isoquinolin–7–ones were coupled with diazotised arylamines to yield orange–red to bluish–red dyes having good coloration properties and excellent fastness to light on polyester fibres. Structure–property relationships in the dyes are discussed with respect to the nature of the substituents in the imide, imidazole and arylazo moieties.